WO2013068389A1 - Verfahren zur herstellung von ameisensäure durch umsetzung von kohlendioxid mit wasserstoff - Google Patents

Verfahren zur herstellung von ameisensäure durch umsetzung von kohlendioxid mit wasserstoff Download PDF

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Publication number
WO2013068389A1
WO2013068389A1 PCT/EP2012/072013 EP2012072013W WO2013068389A1 WO 2013068389 A1 WO2013068389 A1 WO 2013068389A1 EP 2012072013 W EP2012072013 W EP 2012072013W WO 2013068389 A1 WO2013068389 A1 WO 2013068389A1
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WIPO (PCT)
Prior art keywords
alkyl
formic acid
phase
tertiary amine
catalyst
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PCT/EP2012/072013
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German (de)
English (en)
French (fr)
Inventor
Thomas Schaub
Marek Pazicky
Donata Maria Fries
Rocco Paciello
Anton Meier
Original Assignee
Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to CA2854047A priority Critical patent/CA2854047A1/en
Priority to EP12783595.7A priority patent/EP2776448A1/de
Priority to CN201280054841.XA priority patent/CN103917551A/zh
Priority to IN3469DEN2014 priority patent/IN2014DN03469A/en
Priority to RU2014123397/04A priority patent/RU2014123397A/ru
Priority to BR112014010923A priority patent/BR112014010923A2/pt
Priority to KR1020147012260A priority patent/KR20140090183A/ko
Priority to SG11201401103YA priority patent/SG11201401103YA/en
Priority to JP2014540431A priority patent/JP2015502922A/ja
Publication of WO2013068389A1 publication Critical patent/WO2013068389A1/de
Priority to ZA2014/04151A priority patent/ZA201404151B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the invention relates to a process for the preparation of formic acid by reacting carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a transition metal complex compound as catalyst comprising at least one element from the 8th, 9th or 10th group of the periodic table and at least one phosphine ligand with at least one organic Containing at least 13 carbon atoms, a tertiary amine and a polar solvent, to form a formic acid-amine adduct, which is then thermally cleaved to formic acid and the corresponding tertiary amine.
  • Adducts of formic acid and tertiary amines can be thermally cleaved into free formic acid and tertiary amine and therefore serve as intermediates in the preparation of formic acid.
  • Formic acid is an important and versatile product. It is used, for example, for acidification in the production of animal feed, as a preservative, as a disinfectant, as an adjuvant in the textile and leather industry, as a mixture with their salts for de-icing of airplanes and runways and as a synthesis component in the chemical industry.
  • the said adducts of formic acid and tertiary amines can be prepared in various ways, for example (i) by direct reaction of the tertiary amine with formic acid, (ii) by hydrolysis of methyl formate to formic acid in the presence of the tertiary amine, (iii) by catalytic Hydration of carbon monoxide in the presence of the teriary amine or (iv) by hydrogenation of carbon dioxide to formic acid in the presence of the tertiary amine.
  • the latter method of catalytic hydrogenation of carbon dioxide has the particular advantage that carbon dioxide is available in large quantities and is flexible in its source.
  • WO 2010/149507 describes a process for the preparation of formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine, a transition metal catalyst and a high boiling polar solvent with an electrostatic factor> 200 * 10 "30 cm, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol and glycerol to give a reaction mixture which contains the formic acid amine.
  • Adduct containing the tertiary amine, the high-boiling polar solvent and the catalyst The reaction mixture is worked up according to WO 2010/149507 according to the following steps:
  • a disadvantage of the process of WO 2010/149507 is that the separation of the catalyst despite phase separation (step 1)) and extraction (step 2)) is not completely successful, so that contained in the raffinate catalyst traces in the thermal cleavage in the distillation column in step 3 ) catalyze the cleavage of the formic acid-amine adduct to carbon dioxide and hydrogen and the tertiary amine according to the following equation:
  • the object of the present invention is to provide a process for the preparation of formic acid by hydrogenation of carbon dioxide, with which a largely complete separation of the catalyst is made possible.
  • the new method should not or only to a significantly reduced extent have the disadvantages of the prior art and lead to concentrated formic acid in high yield and high purity.
  • the method should allow a simpler process management, as described in the prior art, in particular a simpler process concept for processing the discharge from the hydrogenation reactor, simpler process steps, a smaller number of process stages or simpler apparatus. Furthermore, the method should also be able to be carried out with the lowest possible energy requirement.
  • Solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and a tertiary amine of the general formula (A1) NR 1 R 2 R 3 (A1),
  • R 1 , R 2 , R 3 independently represent an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical each having 1 to 16 carbon atoms, wherein individual carbon atoms independently of one another by a hetero group selected from the groups -O- and > N-substituted may be and two or all three radicals may be connected together to form a chain comprising at least four atoms, in the presence of at least one transition metal complex compound as catalyst, the at least one element selected from groups 8, 9 and 10 of the Periodic Table and at least one phosphine ligand having at least one organic radical having at least 13 carbon atoms, in a hydrogenation reactor to obtain, optionally after addition of water, a biphasic
  • Containing hydrogenation mixture (H) an upper phase (01) containing the catalyst and the tertiary amine (A1), and a lower phase (U 1) containing the at least one polar solvent, residues of the catalyst and a formic acid-amine adduct of the general formula (A2) .
  • X is in the range of 0.4 to 5 and
  • R 1 , R 2 , R 3 have the meanings given above,
  • step (b1) phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U 1), or
  • step (b2) Extraction of the catalyst from the hydrogen mixture (H) obtained in step (a) in an extraction unit with an extractant containing a tertiary amine (A1) to obtain a raffinate (R1) containing the formic acid-amine adduct (A2) and the at least one polar solvent and an extract (E1) containing the tertiary amine (A1) and the
  • step (c) separating the at least one polar solvent from the lower phase (U 1), from the raffinate (R1) or from the raffinate (R2) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is present in the hydrogenation reactor is recycled in step (a), and a biphasic bottoms mixture (S1) comprising an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2) contains
  • step (d) optionally working up of the bottom mixture (S1) obtained in step (c) by phase separation in a second phase separation device into the upper phase (02) and the lower phase (U2),
  • step (e) cleavage of the formic acid-amine adduct (A2) present in the bottom mixture (S1) or optionally in the lower phase (U2) in a thermal splitting unit to give the corresponding tertiary amine (A1) which is added to the hydrogenation reactor in step (a) recycled formic acid, and from formic acid, which is discharged from the thermal cleavage unit.
  • formic acid can be obtained in high yield with the process according to the invention.
  • the process according to the invention makes it possible to remove the transition metal complex compound used as catalyst more effectively than the prior art and to return it to the hydrogenation reactor in step (a).
  • the cleavage of the formic acid-amine adduct (A2) is largely prevented, which leads to an increase in the formic acid yield.
  • the separation of the polar solvent used according to the invention also prevents esterification of the formic acid obtained in the thermal splitting unit in step (e), which likewise leads to an increase in the yield of formic acid.
  • the use of the polar solvents according to the invention leads to an increase in the concentration of the formic acid-amine adduct (A2) in the hydrogenation mixture (H) obtained in step (a) compared to the polar high-boiling solvents used in WO2010 / 149507. leads. This allows the use of smaller reactors, which in turn leads to a cost savings.
  • a reaction mixture (Rg) is reacted in process step (a) in a hydrogenation reactor, the carbon dioxide, hydrogen, at least one polar solvent selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and a tertiary amine of the general formula (A1).
  • the reaction takes place in the presence of a catalyst.
  • a catalyst at least one
  • Transition-metal complex compound containing at least one element selected from Groups 8, 9 and 10 of the Periodic Table and at least one phosphine ligand having at least 13 carbon atoms.
  • the carbon dioxide used in process step (a) can be solid, liquid or gaseous. It is also possible to use gas mixtures containing large quantities of carbon dioxide, provided they are substantially free of carbon monoxide (volume fraction of ⁇ 1% CO).
  • the hydrogen used in the hydrogenation of carbon dioxide in process step (a) is generally gaseous. Carbon dioxide and hydrogen may also contain inert gases, such as nitrogen or noble gases. However, their content is advantageously below 10 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor. While larger amounts may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
  • Carbon dioxide and hydrogen can be fed to process stage (a) as separate streams. It is also possible to use a mixture containing carbon dioxide and hydrogen in process step (a).
  • tertiary amine (A1) is used in process step (a) in the hydrogenation of carbon dioxide.
  • tertiary amine (A1) is understood as meaning both one (1) tertiary amine (A1) and mixtures of two or more tertiary amines (A1).
  • the tertiary amine (A1) used in the process according to the invention is preferably selected or matched with the polar solvent such that the hydrogenation mixture (H) obtained in process step (a) is at least biphasic, if appropriate after the addition of water.
  • the Hydrogenation mixture (H) contains an upper phase (01) containing the catalyst and the tertiary amine (A1), and a lower phase (U 1) containing the at least one polar solvent, residues of the catalyst and a formic acid-amine adduct (A2 ) contains.
  • the tertiary amine (A1) is enriched in the upper phase (01), i. the upper phase (01) contains the main part of the tertiary amine (A1).
  • enriched or “main part” with respect to the tertiary amine (A1) is a weight fraction of the free tertiary amine (A1) in the upper phase (01) of> 50% based on the total weight of the free tertiary Amine (A1) in the liquid phases, ie the upper phase (01) and the lower phase (U 1) in the hydrogenation mixture (H) to understand.
  • free tertiary amine (A1) is meant the tertiary amine (A1) which is not bound in the form of the formic acid-amine adduct (A2).
  • the weight fraction of the free tertiary amine (A1) in the upper phase (01) is preferably> 70%, in particular> 90%, in each case based on the total weight of the free tertiary amine (A1) in the upper phase (01) and the lower phase ( U 1) in the hydrogenation mixture (H).
  • the selection of the tertiary amine (A1) is generally carried out by a simple experiment in which the phase behavior and the solubility of the tertiary amine (A1) in the liquid phases (upper phase (01) and lower phase (U1)) under the process conditions in the process stage (a) be determined experimentally.
  • non-polar solvents such as aliphatic, aromatic or araliphatic solvents may be added to the tertiary amine (A1).
  • Preferred non-polar solvents are, for example, octane, toluene and / or xylenes (o-xylene, m-xylene, p-xylene).
  • tertiary amines of the general formula (A1) in which the radicals R 1 , R 2 , R 3 are identical or different and independently of one another are an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical having in each case 1 to 16 Carbon atoms, preferably 1 to 12 carbon atoms represent, wherein individual carbon atoms can be substituted independently of one another by a hetero group selected from the groups -O- and> N- and two or all three radicals to form a chain comprising at least four atoms also together can be connected.
  • a tertiary amine of the general formula (A1) is used, with the proviso that the total number of carbon atoms is at least 9.
  • suitable tertiary amines (A1) include:
  • triphenylamine methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis (2-ethylhexyl ) - phenylamine, tribenzylamine, methyl-dibenzylamine, ethyl-dibenzylamine and theirs by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2- propyl groups substituted derivatives.
  • Nd-bis-C 1-4 -alkyl-piperidines N, N-di-d-bis-C 1-4 -alkyl-piperazines, N-crib-C 12 -alkyl-pyrrolidones, N-C 1 -C -alkyl-imidazoles and their derivatives one or more methyl. Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2-propyl groups substituted derivatives.
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • DABCO 1, 4-diazabicyclo [2.2.2] octane
  • tropane N-methyl-8-azabicyclo [3.2 .1] octane
  • garnetane N-methyl-9-azabicyclo [3.3.1] nonane
  • 1-azabicyclo [2.2.2] octane quinuclidine
  • mixtures of two or more different tertiary amines (A1) can also be used.
  • tertiary amine (A1) is an amine in which the radicals R 1 , R 2 , R 3 are independently selected from the group C to C 12 alkyl, C 5 - to C 8 - Cycloalkyl, benzyl and phenyl.
  • tertiary amine (A1) is a qesquestionedtiqtes amine, ie only single bonds containing amine.
  • An especially suitable amine in the process according to the invention is a tertiary amine of the general formula (A1) in which the radicals R 1 , R 2 , R 3 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri -n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine.
  • one (1) tertiary amine of the general formula (A1) is used.
  • the tertiary amine used is an amine of the general formula (A1) in which the radicals R 1 , R 2 and R 3 are selected independently of one another from C 5 - and C 6 -alkyl.
  • tri-n-hexylamine is used as the tertiary amine of the general formula (A1).
  • the tertiary amine (A1) in the process according to the invention is preferably liquid in all process stages. However, this is not a mandatory requirement. It would also be sufficient if the tertiary amine (A1) were dissolved at least in suitable solvents.
  • Suitable solvents are in principle those which are chemically inert with respect to the hydrogenation of carbon dioxide, in which the tertiary amine (A1) and the catalyst dissolve well and in which, conversely, the polar solvent and the formic acid-amine adduct (A2) dissolve poorly ,
  • chemically inert, nonpolar solvents such as aliphatic, aromatic or araliphatic hydrocarbons, such as octane and higher alkanes, toluene, xylenes.
  • At least one polar solvent is selected in process step (a) in the hydrogenation of carbon dioxide from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol and water used.
  • polar solvent is understood to mean both one (1) polar solvent and mixtures of two or more polar solvents.
  • the polar solvent is preferably selected so that the hydrogenation mixture (H) obtained in process step (a), if appropriate after the addition of water, is at least biphasic.
  • the polar solvent should be enriched in the lower phase (U 1), ie the lower phase (U 1) should contain the main part of the polar solvent.
  • "enriched" or "main part" with respect to the polar solvent is a weight fraction of the polar solvent in the lower phase (U 1) of> 50% based on the Total weight of the polar solvent in the liquid phases (upper phase (01) and lower phase (U 1)) in the hydrogenation reactor to understand.
  • the weight fraction of the polar solvent in the lower phase (U 1) is preferably> 70%, in particular> 90%, in each case based on the total weight of the polar solvent in the upper phase (01) and the lower phase (U 1).
  • the selection of the polar solvent satisfying the above criteria is generally accomplished by a simple experiment in which the phase behavior and the solubility of the polar solvent in the liquid phases (upper phase (01) and lower phase (U 1)) under the process conditions in Process step (a) are determined experimentally.
  • the polar solvent may be a pure polar solvent or a mixture of two or more polar solvents.
  • step (a) first of all a single-phase hydrogenation mixture is obtained, which is converted into the biphasic hydrogenation mixture (H) by the addition of water.
  • the biphasic hydrogenation mixture (H) is obtained directly in step (a).
  • the biphasic hydrogenation mixture (H) obtained in this embodiment can be directly fed to the work-up of step (b). It is also possible to additionally add Waser to the biphasic hydrogenation mixture (H) before further processing in step (b). This can lead to an increase of the distribution coefficient P K.
  • the polar solvent used is water, methanol or a mixture of water and methanol.
  • diols and their formic acid esters, polyols and their formic acid esters, sulfones, sulfoxides and open-chain or cyclic amides as the polar solvent is not preferred. In a preferred embodiment, these polar solvents are not contained in the reaction mixture (Rg).
  • the molar ratio of the polar solvent or solvent mixture used in the process according to the invention in process step (a) to the tertiary amine (A1) used is generally 0.5 to 30 and preferably 1 to 20.
  • the transition metal complex compound used in the process according to the invention in process step (a) for the hydrogenation of carbon dioxide comprises at least one element selected from groups 8, 9 and 10 of the Periodic Table (IUPAC nomenclature) and at least one phosphine ligand having at least one organic radical having at least 13 carbon atoms , Groups 8, 9 and 10 of the Periodic Table include Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.
  • the catalyst used may be one (1) transition metal complex compound or a mixture of two or more transition metal complex compounds.
  • transition metal complex compound is understood as meaning both one (1) transition metal complex compound and mixtures of two or more transition metal complex compounds.
  • the transition metal complex compound used as a catalyst contains at least one element selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt, more preferably at least one element selected from the group consisting of Ru, Rh and Pd.
  • the transition metal complex compound Ru is preferred as the catalyst include at least one phosphine ligand having at least one organic radical having 13 to 30 carbon atoms, preferably 14 to 26 carbon atoms, more preferably 14 to 22 carbon atoms, more preferably 15 to 22 carbon atoms, especially 16 to 20 carbon atoms the organic radical is bonded to a phosphorus atom of the phosphine ligand.
  • the transition metal complex compounds used as catalyst contain at least one bidentate phosphine ligand of the general formula (I)
  • R 11, R 12, R 13, R 14 independently of one another unsubstituted or at least mono-substituted C 13 -C 3 O-alkyl, - (phenyl) - (4-C 7 -C 2 alkyl), - (phenyl) - (C C 4 -C 24 -alkyl) 2 , - (phenyl) - (C 3 -C 24 -alkyl) 3 , - (phenyl) - (0-C 7 -C 24 -alkyl), - (phenyl) - (0- C 4 -C 24 alkyl) 2, - (phenyl) - (0-C 3 - C 24 alkyl) 3, - (cyclohexyl) - (C 7 -C 24 alkyl), - (cyclohexyl) - (C 4 -
  • substituents are selected from the group consisting of -F, -Cl, -Br, -OH, -OR a , -COOH, -COOR a ,
  • R 15 , R 16 are independently hydrogen or -C- C 4 alkyl or together with the carbon atoms to which they are attached form an unsubstituted or at least monosubstituted phenyl or cyclohexyl ring, the substituents being selected from the group consisting of -OCOR a , -OCOCF 3 , -OSO 2 R a , -OSO 2 CF 3 , -CN, -OH, -OR a , -N (R a ) 2 , -NHR a and -CC 4 -alkyl;
  • R a is -CC 4 alkyl and n, m are independently 0, 1 or 2.
  • R 1 1, R 12, R 13 and R 14 are understood linear or branched alkyl radicals having 13 to 30 carbon atoms in the present invention.
  • radicals include linear or branched alkyl radicals selected from the group consisting of tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl , Hexacosyl, heptacosyl, octacosyl, nonacosyl and tricontyl.
  • the C 13 -C 30 -alkyl radicals are preferably unbranched, ie linear.
  • Preferred alkyl groups (C 13 -C 30 alkyl), linear or branched alkyl radicals having from 14 to 26 (C i -C 4 2 6-alkyl), more preferably having 14 to 22 (- C
  • the -C 7 -C 24 -alkyl radicals can be bonded to the phenyl ring in the 2, 3 or 4 position and may be linear or branched.
  • the phenyl ring preferably carries no further substituents in addition to the -C 7 -C 24 -alkyl radical.
  • the -C 7 -C 2 alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -C 7 -C 24 -alkyl radicals are linear and unsubstituted.
  • alkyl radicals in the - (phenyl) - (C 7 -C 2 4-alkyl) radical preference is given to linear or branched alkyl radicals having 7 to 18 (ie - (phenyl) - (C 7 -C 8 -alkyl)). Particularly preferred are alkyl radicals having 7 to 12 carbon atoms (ie - (phenyl) - (C 7 -C 12 alkyl)).
  • Sub- (phenyl) - (O-C 6 -C 24 -alkyl), with respect to the radicals R 11 , R 12 , R 13 and R 14 , in the context of the present invention are radicals of the general formula (III) which are bound via the phenyl ring to the phosphorus atom of the phosphine ligand (I).
  • the -O-C 7 -C 24 -alkyl radicals can be bonded to the phenyl ring in 2, 3 or 4 position via the oxygen and can be linear or branched.
  • the phenyl ring preferably carries no further substituents in addition to the -C 7 -C 24 -alkyl radical.
  • the -O-C 7 -C 24 -alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -C 7 -C 24 -alkyl radicals are linear and unsubstituted.
  • Alkyl radicals in the - (phenyl) - (O-C 7 -C 24 -alkyl) radical are linear or branched alkyl radicals having 7 to 18 carbon atoms (ie - (phenyl) - (0-C 7 -C 18 -alkyl )) prefers.
  • Particularly preferred are alkyl radicals having 7 to 12 carbon atoms (ie - (phenyl) - (0-C 7 -C 12 alkyl)).
  • the -C 7 -C 24 -alkyl radicals can be bonded to the cyclohexyl ring in the 2, 3 or 4 position and can be linear or branched.
  • the cyclohexyl ring preferably carries no further substituents in addition to the -C 7 -C 24 -alkyl radical.
  • the -C 7 -C 24 -alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -C 7 -C 24 -alkyl radicals are linear and unsubstituted.
  • alkyl radicals in the - (cyclohexyl) - (C 7 -C 24 -alkyl) radical preference is given to linear or branched alkyl radicals having 7 to 18 carbon atoms (ie - (cyclohexyl) - (C 7 -C 18 -alkyl)).
  • Particularly preferred are alkyl radicals having 7 to 12 carbon atoms (ie, - (cyclohexyl) - (C 7 -C 12 alkyl)).
  • sub- (cyclohexyl) -O-C 7 -C 24 -alkyl are radicals of the general formula (V) which the cyclohexyl ring (wavy bond, 1 position) are bonded to the phosphorus atom of the phosphane ligand (I).
  • the -O-C 7 -C 24 -alkyl radicals are attached to the Cylclohexylring in 2, 3 or 4 position via the oxygen and may be linear or branched.
  • the cyclohexyl ring preferably carries no further substituents in addition to the -C 7 -C 24 -alkyl radical.
  • the -O-C 7 -C 24 -alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -C 7 -C 24 -alkyl radicals are linear and unsubstituted.
  • Alkyl radicals in the - (cyclohexyl) - (O-C 7 -C 24 -alkyl) radical are linear or branched alkyl radicals having 7 to 18 carbon atoms (ie (Cyclohexyl) - (0-C 7 -C 18 alkyl)).
  • Particularly preferred are alkyl radicals having 7 to 12 carbon atoms (ie, - (cyclohexyl) - (O-C 7 -C 12 -alkyl)).
  • the C 7 -C 24 -alkyl or the -0-C 7 -C 24 -alkyl radicals are preferably bonded in the 4 position to the phenyl rings or the cyclohexyl rings.
  • the phenyl or cyclohexyl rings carry in position 4 a C 7 -C 18 - alkyl or a -0-C 7 -C 18 alkyl radical.
  • the phenyl rings or the cyclohexyl rings in the 4 position carry a -C 7 -C 12 -alkyl or a -O-C 7 -C 12 -alkyl radical.
  • radicals are understood which via the phenyl ring to the phosphorus atom of the phosphine ligand (I) are bonded and the phenyl ring carries two -C 4 -C 24 alkyl radicals.
  • the -C 4 -C 24 -alkyl radicals can be in (2, 3) -, (2, 4) -, (2, 5) -, (2, 6) -, (3, 4) - or (3 5) position to the phenyl ring, with the (3, 5) position being preferred.
  • the -C 4 -C 24 -alkyl radicals can be linear or branched.
  • the phenyl ring preferably carries no further substituents in addition to the two C 4 -C 24 -alkyl radicals.
  • the -C 4 -C 24 -alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -C 4 -C 24 -alkyl radicals are unsubstituted.
  • alkyl radicals in the - (phenyl) - (C 4 -C 24 -alkyl) 2 radical preference is given to linear or branched alkyl radicals having 4 to 18 (ie - (phenyl) - (C 4 -C 18 -alkyl)) 2 , Particularly preferred are alkyl radicals having 4 to 12 carbon atoms (ie - (phenyl) - (C 4 -C 12 alkyl)) 2 and especially having 4 to 6 carbon atoms (ie - (phenyl) - (C 4 -C 6 -) Alkyl)) 2 .
  • a suitable alkyl radical is, for example, tert-butyl.
  • Sub - - (phenyl) - (0-C 4 -C 24 -alkyl) 2 are understood in the context of the present invention radicals which via the phenyl ring the phosphorus atom of the phosphine ligand (I) are bonded and the phenyl ring carries two -QC 4 -C 24 alkyl radicals.
  • the -QC 4 -C 24 -alkyl radicals may be in (2, 3) -, (2, 4) -, (2, 5), (2, 6), (3, 4) or (3, 5) position may be bonded to the phenyl ring, with the (3, 5) position being preferred.
  • the -O-C 4 -C 2 4 alkyl radicals may be linear or branched.
  • the phenyl ring preferably carries no further substituents besides the two -O-C 4 -C 24 -alkyl radicals.
  • the -O-C 4 -C 24 -alkyl radicals may be unsubstituted or at least monosubstituted.
  • the -0-C 4 -C 24 alkyl radicals are preferably unsubstituted.
  • Alkyl radicals in the - (phenyl) - (0-C 4 -C 24 alkyl) 2 radical are linear or branched alkyl radicals having 4 to 18 (ie - (phenyl) - (0-C 4 -C 8 -alkyl )) 2 preferred.
  • a suitable -O-alkyl radical is, for example, tert-butoxy.
  • Sub - (phenyl) - (C 3 -C 24 alkyl) 3 , - (phenyl) - (O-C 3 -C 24 alkyl) 3 , - (cyclohexyl) - (C 3 -C 24 alkyl) 3 , - (Cyclohexyl) - (0-C 3 -C 24 alkyl) and (cyclohexyl) - (0-C 3 -C 24 alkyl) 3 are phenyl or cyclohexyl understood that in position 1 to the phosphorus atom of the phosphine ligand (I) are bonded and the phenyl or cyclohexyl ring carries three -C 3 - C 24 alkyl radicals or three -O-C 3 -C 24 alkyl radicals.
  • the C 3 -C 24 alkyl or -0-C 3 - C 24 alkyl radicals may in (2,3,4) - (2,3,5) - (2,4,6) - , (3,4,5) - or (2,3,6) -position to be bound to the phenyl or cyclohexyl ring.
  • Particularly preferred are phosphine ligands (I) in which the radicals R 11 , R 12 , R 13 and R 14 are the same.
  • phosphine ligands of the general formula (I) in which
  • R 11 , R 12 , R 13 , R 14 independently of one another are unsubstituted or at least monosubstituted C 13 -C 30 -alkyl, - (phenyl) - (C 7 -C 24 -alkyl), - (phenyl) - (C 4 - C 24 -alkyl) 2 , - (phenyl) - (0-C 7 -C 24 -alkyl), - (phenyl) - (O-C 4 -C 24 -alkyl) 2 , - (cyclohexyl) - (C 7 -C 24 alkyl), - (cyclohexyl) - (C 4 -C 24 alkyl) 2 , - (cyclohexyl) - (0 -C 7 -C 24 alkyl) or - (cyclohexyl) - (0 -C 4 -C 24 -
  • substituents are selected from the group consisting of -F, -Cl, -Br, -OH, -OR a , -COOH, -COOR a , -OCOR a , -CN, -NH 2 , -N (R a ) 2 and -NHR a ;
  • R 15 , R 16 are each, independently of one another, hydrogen or C 1 -C 4 -alkyl or together with the carbon atoms to which they are attached, form an unsubstituted or at least monosubstituted phenyl or cyclohexyl ring,
  • substituents are selected from the group consisting of -OCOR a , -OCOCF 3 , -OSO 2 R a , -OSO 2 CF 3 , -CN, -OH, -OR a , -N (R a ) 2 , -NHR a and -CC 4 -alkyl;
  • R a is -CC 4 alkyl and n, m are both 0, 1 or 2, preferably both 0 or 1, especially both 0.
  • substituents are selected from the group consisting of -F, -Cl, -Br, -OH, -OR a , -COOH, -COOR a ,
  • R 15 , R 16 are each, independently of one another, hydrogen or C 1 -C 4 -alkyl or together with the carbon atoms to which they are attached form an unsubstituted or at least monosubstituted phenyl or cyclohexyl ring,
  • substituents are selected from the group consisting of -OCOR a , -OCOCF 3 , -OSO 2 R a , -OSO 2 CF 3 , -CN, -OH, -OR a , -N (R a ) 2 , -NHR a and -CC 4 -alkyl;
  • R a is -CC 4 alkyl and n, m are both 0, 1 or 2, preferably both 0 or 1, especially both 0.
  • phosphine ligands of the general formula (I) in which
  • R 11 , R 12 , R 13 , R 14 independently of one another are unsubstituted or at least monosubstituted C 13 -C 30 -alkyl, wherein the substituents are selected from the group consisting of -F, -Cl, -Br, -OH, -OR a , -COOH, -COOR a , -OCOR a , -CN, -NH 2 , -N (R a ) 2 and -NHR a ;
  • R 15 , R 16 independently of one another are hydrogen or -Ci-C 4 -alkyl
  • R a is -Ci-C 4 alkyl and n, m are both 0.
  • phosphine ligands of the general formula (I) in which
  • R 11 , R 12 , R 13 , R 14 are independently unsubstituted -C 3 C 30 alkyl
  • R 15 , R 16 are both hydrogen and n, m are both 0.
  • Most preferred are phosphine ligands of the general formula (I) in which
  • R 11 , R 12 , R 13 , R 14 are all the same unsubstituted C 12 -C 20 alkyl, preferably unsubstituted C 12 -C 18 alkyl and more preferably C 13 -C 18 alkyl;
  • Particularly preferred bidentate phosphine ligands (I) are selected from the group consisting of 1, 2-bis (ditetradecylphosphino) ethane, 1, 2-bis (dipentadecylphosphino) ethane, 1 , 2-bis (dihexadecylphosphino) ethane and 1, 2-bis (dioctadecylphosphino) ethane.
  • R 15 and R 16 in formula (VI II) the definitions and preferences given for the phosphine ligand (I) apply accordingly.
  • Phosphane ligands of the general formula (I) in which n and m are both 0 and in which R 11 , R 12 , R 13 and R 14 are each independently unsubstituted or at least monosubstituted -C 12 -C 30 -alkyl, are furthermore, for example by reacting 1, 2-bis (dihydrophosphino) ethane compounds of the general formula (X) with terminal olefins of the general formula (XI) according to the following reaction equation 2 (RG 2) accessible, wherein in the formulas (XI) and (I) R 18 apply the meanings and preferences given above for R 11 , R 12 , R 13 , R 14 mutatis mutandis.
  • R 15 and R 16 in formula (X) the definitions and preferences given for the phosphine ligand (I) apply accordingly.
  • the phosphine ligands (I) in which n and m are both 0 are moreover accessible, for example, by reacting monophosphane compounds of the general formula (XII) with alkyne compounds of the general formula (XI II) according to the following reaction equation 3 (RG 3) in the formulas (XI I) and (I) R 17 has the meanings given above for R 11 , R 12 , R 13 , R 14 , the preferences apply accordingly.
  • R 15 and R 16 in formula (XI II) apply the definitions and preferences given for the phosphine ligand (I) accordingly.
  • the transition metal complex compounds used as catalyst contain one (1) bidentate phosphine ligand of the general formula (I) and at least one monodentate monophosphine ligand having at least one organic radical having from 1 to 20 carbon atoms.
  • denticity is understood to mean the number of bonds which the phosphane ligand can form to the transition metal central atom from a phosphorus atom of the phosphine ligand. That monodentate phosphine ligands can form a bond from the phosphorus atom to the transition metal central atom, bidentate phosphine ligands can form two bonds from the phosphorous atoms to the transition metal central atom.
  • R 19 , R 20 , R 21 are independently unsubstituted or at least monosubstituted C 1 -C 2 o-alkyl, phenyl, benzyl, cyclohexyl or - (CH 2 ) cyclohexyl, wherein the substituents are selected from the group consisting of -d-Czo-alkyl, -F, -Cl, -Br, -OH, -OR a , -COOH, -COOR a , -OCOR a , -CN, -NH 2, -N (R a ) 2 and -NHR a ; Is -CC 4 alkyl.
  • the -C 1 -C 2 o-alkyl may be linear or branched.
  • Suitable radicals for R 19 , R 20 , R 21 are, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1- (2-methyl) propyl, 2- (2-methyl) propyl, 1 -Pentyl, 1 -hexyl, 1-heptyl, 1-octyl, 1 -nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl , 1-octadecyl, 1-nonadecyl, 1-lcosyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, methylcyclopentyl, methyl
  • Monosubstituted monophosphane ligands (Ia) in which the three radicals R 19 , R 20 , R 21 are identical are preferred. Particular preference is given to mononuclear monophosphine ligands (Ia) of the formula P (nC q H 2 q + i) 3 with q equal to 1 to 20, in particular with q equal to 1 to 12.
  • the mononuclear monophosphane ligand (Ia) is selected from the group consisting of tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tri-n-decylphosphine and tri-n-dodecylphosphine.
  • the transition metal complex compound used as a catalyst preferably contains a bidentate phosphine ligand (I) and two monodentate monophosphine ligands (Ia), with the definitions and preferences given above for the bidentate phosphine ligands (I) and monodentate monophosphane ligands (Ia).
  • the transition metal complex compound may further contain other ligands exemplified by hydride, fluoride, chloride, bromide, iodide, formate, acetate, propionate, carboxylate, acetylacetonate, carbonyl, DMSO, hydroxide, trialkylamine, alkoxide.
  • ligands exemplified by hydride, fluoride, chloride, bromide, iodide, formate, acetate, propionate, carboxylate, acetylacetonate, carbonyl, DMSO, hydroxide, trialkylamine, alkoxide.
  • the transition metal complex compounds used as catalyst can be used both directly in their active form and starting from customary standard complexes such as [M (p-cymene) Cl 2 ] 2, [M (benzene) Cl 2 ] n , [M (COD) (allyl) ], [MCI 3 x H 2 0], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M (DMSO) 4 Cl 2 ] with M being the same as element from the 8th, 9th or 10.
  • Group of the periodic table with the addition of the corresponding or the corresponding phosphine only under reaction conditions in process step (a) (in situ) are generated.
  • the catalyst used is preferably at least one transition metal complex compound selected from the group consisting of [Ru (P n Bu 3 ) 2 (1,2-bis (ditetradecylphosphino) ethane) (H) 2 ],
  • homogeneous catalysis is understood as meaning that the catalyst is at least partially dissolved in the liquid reaction medium.
  • at least 90% of the catalyst used in process step (a) is dissolved in the liquid reaction medium, more preferably at least 95%, particularly preferably more than 99%, most preferably the catalyst is completely dissolved in the liquid reaction medium (100%). ), in each case based on the total amount of catalyst present in the liquid reaction medium (liquid phases of the reaction mixture (Rg)).
  • the amount of the metal component of the transition metal complex compound used as catalyst in process step (a) is generally from 0.1 to 5000 ppm by weight, preferably from 1 to 800 ppm by weight, and more preferably from 5 to 800 ppm by weight, based in each case entire liquid reaction mixture (Rg) in the hydrogenation reactor.
  • the catalyst is selected so that it is enriched in the upper phase (01), ie the upper phase (01) contains the main part of the catalyst.
  • a distribution coefficient P K of> 50 is preferred and a distribution coefficient P K of> 100 is particularly preferred.
  • the present invention therefore also provides the transition metal complex compound and its use as a catalyst, in particular as a catalyst in a process for the preparation of formic acid.
  • the present invention thus also provides a transition metal complex compound containing at least one element selected from Groups 8, 9 and 10 of the Periodic Table and at least one phosphine ligand of the general formula (I).
  • the present invention thus also provides a transition metal complex compound which comprises a phosphine ligand of the general formula (I) and at least one monodentate phosphine ligand of the general formula (Ia).
  • the present invention thus also relates to the use of the transition metal complex compound as catalyst in a process for the preparation of formic acid.
  • the hydrogenation of carbon dioxide in process step (a) is preferably carried out in the liquid phase at a temperature in the range of 20 to 200 ° C and a total pressure in the range of 0.2 to 30 MPa abs.
  • the temperature is at least 30 ° C and more preferably at least 40 ° C and preferably at most 150 ° C, more preferably at most 120 ° C and most preferably at most 80 ° C.
  • the total pressure is preferably at least 1 MPa abs and more preferably at least 5 MPa abs and preferably at most 20 MPa abs.
  • the hydrogenation is carried out in process step (a) at a temperature in the range of 40 to 80 ° C and a pressure in the range of 5 to 20 MPa abs.
  • the partial pressure of the carbon dioxide in process step (a) is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
  • the hydrogenation in process step (a) is carried out at a partial pressure of the carbon dioxide in the range of 2 to 7.3 MPa.
  • the partial pressure of the hydrogen in process step (a) is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 15 MPa.
  • the hydrogenation in process step (a) is carried out at a partial pressure of the hydrogen in the range of 1 to 15 MPa.
  • the molar ratio of hydrogen to carbon dioxide in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 1 to 3.
  • the molar ratio of carbon dioxide to tertiary amine (A1) in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 0.5 to 3.
  • reactors which are suitable for gas / liquid reactions under the given temperature and the given pressure can be used as hydrogenation reactors.
  • Suitable standard reactors for gas-liquid reaction systems are, for example, in KD Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.b04_087, Chapter 3.3 "Reactors for gas-liquid reactions" indicated.
  • stirred tank reactors tubular reactors or bubble column reactors.
  • the hydrogenation of carbon dioxide can be carried out batchwise or continuously in the process according to the invention.
  • the reactor is equipped with the desired liquid and optionally solid feedstocks and auxiliaries, and then carbon dioxide and the polar solvent are pressed to the desired pressure at the desired temperature.
  • the reactor is normally depressurized and the two liquid phases formed are separated from one another.
  • the feedstocks and auxiliaries, including carbon dioxide and hydrogen are added continuously. Accordingly, the liquid phases are continuously discharged from the reactor, so that the liquid level in the reactor remains the same on average. Preference is given to the continuous hydrogenation of carbon dioxide.
  • the average residence time of the components in the hydrogenation reactor contained in the reaction mixture (Rg) is generally from 5 minutes to 5 hours.
  • a hydrogenation mixture (H) is obtained in process step (a) which contains the catalyst, the polar solvent, the tertiary amine (A1) and the at least one formic acid-amine adduct (A2).
  • formic acid-amine adduct (A2) is understood as meaning both one (1) formic acid-amine adduct (A2) and mixtures of two or more formic acid-amine adducts (A2) or more formic acid-amine adducts (A2) are obtained in process step (a), if in the reaction mixture used (Rg) two or more tertiary amines (A1) are used.
  • a reaction mixture (Rg) is used in process step (a) which comprises a (1) tertiary amine (A1), a hydrogenation mixture (H) being obtained which comprises one (1) formic acid amine.
  • Adduct (A2) contains.
  • a reaction mixture (Rg) is used in process step (a) which comprises tri-n-hexylamine as the tertiary amine (A1) to give a hydrogenation mixture (H) which comprises the formic acid amine.
  • Adduct of tri-n-hexylamine and formic acid corresponds to the following formula (A3)
  • x is in the range of 0.4 to 5.
  • the factor X indicates the average composition of the formic acid-amine adduct (A2) and (A3), respectively. the ratio of bound tertiary amine (A1) to bound formic acid in the formic acid-amine adduct (A2) or (A3).
  • the factor x can be determined, for example, by determining the formic acid content by acid-base titration with an alcoholic KOH solution against phenolphthalein. In addition, a determination of the factor x, by determining the amine content by gas chromatography is possible.
  • the exact composition of the formic acid-amine adduct (A2) or (A3) depends on many parameters, such as the concentrations of formic acid and tertiary amine (A1), the pressure, the temperature and the presence and nature of other components, in particular of the polar solvent.
  • the composition of the formic acid-amine adduct (A2) or (A3), i. of the factor x , also change over the individual process stages. For example, after removal of the polar solvent, a formic acid-amine adduct (A2) or (A3) with a higher formic acid content generally forms, the excess bound tertiary amine (A1) being formed from the formic acid-amine adduct (A2 ) is split off and forms a second phase.
  • a formic acid-amine adduct (A2) or (A3) is generally obtained in which x is in the range from 0.4 to 5, preferably in the range from 0.7 to 1.6 ,
  • the formic acid-amine adduct (A2) is enriched in the lower phase (U 1), ie the lower phase (U 1) contains the main part of the formic acid-amine adduct (A2).
  • the weight fraction of the formic acid-amine adduct (A2) in the lower phase (U 1) is preferably> 70%, in particular> 90%, in each case based on the total weight of the formic acid-amine adduct (A2) in the upper phase (01 ) and the lower phase (U 1).
  • the hydrogenation mixture (H) obtained in the hydrogenation of carbon dioxide in process step (a) preferably has, after addition of water, two liquid phases and is in process step (b) according to one of the steps (b1), (b2) or (b3) further worked up.
  • the hydrogenation mixture (H) obtained in process step (a) is further worked up in a first phase separation device by phase separation to obtain a lower phase (U 1) containing the formic acid-amine adduct (A2) containing at least one polar solvent and residues of the catalyst and an upper phase (01) containing the catalyst and the tertiary amine (A1).
  • the amount of the metal component of the catalyst contained in the lower phase (U 1) is generally less than 4 ppm by weight, preferably less than 3 ppm by weight, more preferably less than 2 ppm by weight and particularly preferably less than 1 wt . ppm, in each case based on the lower phase (U 1).
  • residues of the catalyst from the lower phase (U 1) can be further depleted by subsequent extraction (workup according to process step b3). Due to the significantly improved distribution coefficients (P K ), the separation of the transition metal compound used as a catalyst succeeds By phase separation largely complete, so that can be dispensed with a subsequent extraction.
  • the upper phase (01) is recycled to the hydrogenation reactor.
  • the lower phase (U 1) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
  • a return of a liquid phase present over both further liquid phase containing unreacted carbon dioxide and a gas phase containing unreacted carbon dioxide and / or unreacted hydrogen to the hydrogenation reactor is advantageous.
  • phase separators are, for example, standard apparatuses and standard methods, which are described, for example, in E. Müller et al., "Liquid-liquid Extraction", in Ullman's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 /14356007.b93_06, Chapter 3 "Apparatus”.
  • the phase separation may take place, for example, after relaxation to about or near atmospheric pressure and cooling of the liquid hydrogenation mixture, for example at about or near ambient temperature.
  • the polar solvent and the tertiary amine (A1) can be selected so that the separation of the lower phase (U 1) enriched with the formic acid-amine adducts (A2) and the polar solvent from the tertiary amine (A1 ) and catalyst-enriched upper phase (01) and the return of the upper phase (01) to the hydrogenation reactor can be carried out at a pressure of 1 to 30 MPa abs.
  • the pressure is preferably at most 20 MPa abs.
  • the process according to the invention is carried out in such a way that the pressure and the temperature in the hydrogenation reactor and in the first phase separator are the same or approximately the same, whereby a pressure difference of up to +/- 0.5 MPa or approximately equal to a temperature difference of up to +/- 10 ° C is understood.
  • the hydrogenation mixture (H) is worked up further in step (b3).
  • the hydrogenation mixture (H) obtained in process step (a) is separated into the lower phase (U 1) and the upper phase (01), which is recycled to the hydrogenation reactor, as described above for process step (b1) in the first phase separation device.
  • the statements and preferences made for process step (b1) apply correspondingly to process step (b3).
  • the hydrogenation reactor simultaneously acts as the first phase separation device. The upper phase (01) then remains in the hydrogenation reactor and the lower phase (U 1) is fed to the extraction unit.
  • the lower phase (U 1) obtained after phase separation is subsequently subjected in an extraction unit to extraction with a tertiary amine (A1) as extractant to remove the residues of the catalyst to obtain a raffinate (R2) containing the formic acid-amine adduct (A2). and the at least one polar solvent and an extract (E2) containing the tertiary amine (A1) and the residues of the catalyst.
  • a tertiary amine (A1) used in process step (a) in the reaction mixture (Rg) is used as extractant, so that the statements and preferences with respect to the tertiary amine (A) for the process step (a) A1) apply correspondingly to process step (b3).
  • the extract (E2) obtained in process step (b3) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the catalyst.
  • the raffinate (R2) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
  • the extractant used in process step (b3) is preferably the tertiary amine (A1) which is obtained in the thermal splitting unit in process step (e).
  • the tertiary amine (A1) obtained in the thermal splitting unit in process step (e) is recycled to the extraction unit in process step (b3).
  • the extraction is carried out in process step (b3) generally at temperatures in the range of 0 to 150 ° C, preferably in the range of 30 to 100 ° C and pressures in the range of 0, 1 to 8 MPa.
  • the extraction can also be carried out under hydrogen pressure.
  • the extraction of the catalyst may be carried out in any suitable apparatus known to those skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns.
  • fractions of individual components of the polar solvent from the lower phase (U 1) to be extracted in the extraction agent, the tertiary amine (A1), are also dissolved.
  • the hydrogenation mixture (H) is further worked up according to step (b2).
  • the hydrogenation mixture (H) obtained in process step (a) is fed as a whole directly to the extraction unit without prior phase separation.
  • the hydrogenation mixture (H) is in this case subjected in an extraction unit to extraction with a tertiary amine (A1) as extractant to remove the catalyst to obtain a raffinate (R1) containing the formic acid-amine adduct (A2) and the at least one polar solvent and an extract (E1) containing the tertiary amine (A1) and the catalyst.
  • a tertiary amine (A1) used in process step (a) in the reaction mixture (Rg) is used as extractant, so that the statements and preferences with respect to the tertiary amine (A) for the process step (a) A1) apply correspondingly to process step (b2).
  • the extract (E1) obtained in process step (b2) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the catalyst.
  • the raffinate (R1) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
  • the tertiary amine (A1) which is obtained in the thermal splitting unit in process step (e) is preferably used as extractant in process step (b2).
  • the tertiary amine (A1) obtained in the thermal splitting unit in process step (e) is recycled to the extraction unit in process step (b2).
  • the extraction is carried out in process step (b2) generally at temperatures in the range of 0 to 150 ° C, preferably in the range of 30 to 100 ° C and pressures in the range of 0, 1 to 8 MPa.
  • the extraction can also be carried out under hydrogen pressure.
  • the extraction of the catalyst may be carried out in any suitable apparatus known to those skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns.
  • the polar solvent is separated off from the lower phase (U 1), from the raffinate (R 1) or from the raffinate (R 2) in a first distillation apparatus.
  • a distillate (D1) and a two-phase bottoms mixture (S1) are obtained.
  • the distillate (D1) contains the separated polar solvent and, in a preferred embodiment, is recycled to the hydrogenation reactor in step (a).
  • the bottoms mixture (S1) contains the upper phase (02), which contains the tertiary amine (A1), and the lower phase (U2), which contains the formic acid-amine adduct (A2).
  • the polar solvent in the first distillation apparatus in process stage (c), the polar solvent is partly removed, so that the bottom mixture (S1) contains not yet separated polar solvent.
  • process step (c) for example, from 5 to 98% by weight of the polar solvent contained in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably 50 to 98% by weight, more preferably 80 to 98 wt .-% and particularly preferably 80 to 90 wt .-% are separated, in each case based on the total weight of the in the lower phase (U 1) in the raffinate (R1) or in the raffinate (R2) polar solvent.
  • the polar solvent is completely separated off in the first distillation apparatus in process stage (c).
  • “completely separated off” is a separation of more than 98% by weight of the polar solvent present in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably more than 98.5 wt .-%, particularly preferably more than 99 wt .-%, in particular more than 99.5 wt .-%, understood, in each case based on the total weight of the in the lower phase (U 1), in the raffinate (R1) or in the raffinate (R2) contained polar solvent.
  • the distillate (D1) separated in the first distillation apparatus is recycled in a preferred embodiment to the hydrogenation reactor in step (a).
  • the separation of the polar solvent from the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2) can be carried out, for example, in an evaporator or in a distillation unit consisting of evaporator and column, the column containing packings, fillers and / or trays filled, done.
  • the at least partial removal of the polar solvent preferably takes place at a bottom temperature at which no free formic acid is formed from the formic acid-amine adduct (A2) at a given pressure.
  • the factor x, of the formic acid-amine adduct (A2) in the first distillation apparatus is generally in the range of 0.4 to 3, preferably in the range of 0.6 to 1, 8, particularly preferably in the range of 0.7 to 1, 7.
  • the bottom temperature in the first distillation apparatus is at least 20 ° C, preferably at least 50 ° C and more preferably at least 70 ° C, and generally at most 210 ° C, preferably at most 190 ° C.
  • the temperature in the first distillation apparatus is generally in the range of 20 ° C to 210 ° C, preferably in the range of 50 ° C to 190 ° C.
  • the pressure in the first distillation apparatus is generally at least 0.001 MPa abs, preferably at least 0.005 MPa abs and more preferably at least 0.01 MPa abs and generally at most 1 MPa abs and preferably at most 0.1 MPa abs.
  • the pressure in the first distillation apparatus is generally in the range of 0.0001 MPa abs to 1 MPa abs, preferably in the range of 0.005 MPa abs to 0.1 MPa abs and more preferably in the range of 0.01 MPa abs to 0.1 MPa abs.
  • the formic acid-amine adduct (A2) and free tertiary amine (A1) can be obtained in the bottom of the first distillation apparatus, since in the removal of the polar solvent formic acid-amine adducts (A2) with lower amine content arise. This forms a bottom mixture (S1) which contains the formic acid-amine adduct (A2) and the free tertiary amine (A1).
  • the bottom mixture (S1) contains, depending on the separated amount of the polar solvent, the formic acid-amine adduct (A2) and optionally the free tertiary amine (A1) formed in the bottom of the first distillation apparatus. If appropriate, the bottoms mixture (S1) is further worked up in process step (d) for further work-up and then fed to process step (e). It is also possible to feed the bottoms mixture (S1) from process step (c) directly to process step (e).
  • the bottoms mixture (S1) obtained in step (c) can be separated into the upper phase (02) and the lower phase (U2) in a second phase separation device.
  • the lower phase (U2) is then further worked up according to process step (e).
  • the upper phase (02) from the second phase separation device is recycled to the hydrogenation reactor in step (a).
  • the upper phase (02) is recycled from the second phase separation apparatus to the extraction unit.
  • the statements and preferences for the first phase separation device apply accordingly.
  • the method according to the invention thus comprises the steps (a), (b1), (c), (d) and (e).
  • the method according to the invention comprises the steps (a), (b2), (c), (d) and (e). In a further embodiment, the method according to the invention comprises the steps (a), (b3), (c), (d) and (e). In a further embodiment, the method according to the invention comprises the steps (a), (b1), (c) and (e). In a further embodiment, the method according to the invention comprises the steps (a), (b2), (c) and (e). In a further embodiment, the method according to the invention comprises the steps (a), (b3), (c) and (e).
  • the method according to the invention consists of the steps (a), (b1), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b2), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b3), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b1), (c) and (e).
  • the process according to the invention consists of the steps (a), (b2), (c) and (e).
  • the process according to the invention consists of the steps (a), (b3), (c) and (e).
  • the bottom mixture (S1) obtained according to step (c) or the lower phase (U2) optionally obtained after the work-up according to step (d) is fed to a thermal splitting unit for further reaction.
  • the formic acid-amine adduct (A2) present in the bottom mixture (S1) or optionally in the bottom phase (U2) is cleaved in the thermal splitting unit to give formic acid and the corresponding tertiary amine (A1).
  • the formic acid is discharged from the thermal splitting unit.
  • the tertiary amine (A1) is recycled to the hydrogenation reactor in step (a).
  • the tertiary amine (A1) from the thermal cleavage unit can be recycled directly to the hydrogenation reactor. It is also possible to initially recycle the tertiary amine (A1) from the thermal splitting unit to the extraction unit in process stage (b2) or process stage (b3) and then to pass it on from the extraction unit to the hydrogenation reactor in step (a); this embodiment is preferred.
  • the thermal splitting unit comprises a second distillation apparatus and a third phase separation apparatus, wherein the cleavage of the formic acid-amine adduct (A2) is carried out in the second distillation apparatus to obtain a distillate (D2) containing formic acid and the second Distillation apparatus is discharged (taken), and a biphasic bottom mixture (S2) containing an upper phase (03) containing the tertiary amine (A1), and a lower phase (U3) containing the formic acid-amine adduct (A2).
  • the removal of the formic acid from the second distillation apparatus obtained in the second distillation apparatus can be carried out, for example, (i) overhead, (ii) overhead and via a side draw, or (iii) only a side draw. If the formic acid is removed overhead, formic acid with a purity of up to 99.99% by weight is obtained. When taken off via a side draw, aqueous formic acid is obtained, in which case a mixture with about 85% by weight of formic acid is particularly preferred. Depending on the water content of the sludge mixture (S1) or, if appropriate, the lower phase (U2) fed to the thermal splitting unit, the formic acid can be withdrawn increasingly as top product or reinforced via the side draw.
  • S1 sludge mixture
  • U2 the lower phase fed to the thermal splitting unit
  • thermal cleavage of the formic acid-amine adduct (A2) is generally carried out according to the process parameters known in the prior art with respect to pressure, temperature and apparatus design. These are described, for example, in EP 0 181 078 or WO 2006/021 41 1.
  • distillation columns are suitable, which generally contain packing, packings and / or trays.
  • the bottom temperature in the second distillation apparatus is at least 130 ° C, preferably at least 140 ° C and more preferably at least 150 ° C, and generally at most 210 ° C, preferably at most 190 ° C, particularly preferably at most 185 ° C.
  • the pressure in the second distillation apparatus is generally at least 1 hPa abs, preferably at least 50 hPa abs and more preferably at least 100 hPa abs, and generally at most 500 hPa, more preferably at most 300 hPa abs and more preferably at most 200 hPa abs.
  • the bottoms mixture (S2) obtained in the bottom of the second distillation apparatus is biphasic.
  • the bottoms mixture (S2) is fed to the third phase separation device of the thermal splitting unit and there in the upper phase (03) containing the tertiary amine (A1), and the lower phase (U3), the formic acid-amine adduct ( A2), separated.
  • the upper phase (03) is discharged from the third phase separator of the thermal splitting unit and recycled to the hydrogenation reactor in step (a).
  • the recycling can be carried out directly to the hydrogenation reactor in step (a) or the upper phase (03) is first the extraction unit in step (b2) or step (b3) and fed from there to Hydrogenation reactor in step (a) forwarded.
  • the lower phase (U3) obtained in the third phase separation device is then supplied again to the second distillation device of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is then subjected to further cleavage in the second distillation apparatus, again giving formic acid and free tertiary amine (A1) and again in the bottom of the second distillation unit of the thermal splitting unit forming a two-phase bottoms mixture (S2), which is then fed again to the third phase separation device of the thermal splitting unit for further processing.
  • the feeding of the bottom mixture (S1) or optionally of the bottom phase (U2) to the thermal splitting unit in process step (e) can take place in the second distillation device and / or the third phase separation device.
  • the feed of the bottom mixture (S1) or optionally the lower phase (U2) in the second distillation device of the thermal separation unit takes place.
  • the feed of the bottom mixture (S1) or optionally the lower phase (U2) takes place both in the second distillation device of the thermal splitting unit, as well as in the third phase separation device of the thermal splitting unit.
  • the bottoms mixture (S1) or optionally the lower phase (U2) is divided into two partial streams, wherein a partial stream of the second distillation apparatus and a partial stream of the third phase separator are fed to the thermal splitting unit.
  • FIG. 1 shows a block diagram of a preferred embodiment of the method according to the invention
  • FIG. 2 shows a block diagram of a further preferred embodiment of the method according to the invention.
  • FIG. 1 I-1 hydrogenation reactor
  • the hydrogenation reactor 1-1 carbon dioxide and hydrogen are reacted in the presence of a tertiary amine (A1), a polar solvent and a transition metal complex compound as a catalyst.
  • a two-phase hydrogenation mixture (H) which has an upper phase (01) comprising the catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2 ) contains.
  • the lower phase (U 1) is supplied as stream 3 to the distillation apparatus 11-1.
  • the upper phase (01) remains in the hydrogenation reactor 1-1.
  • the hydrogenation reactor 1-1 simultaneously acts as the first phase separation device.
  • the lower phase (U 1) is separated into a distillate (D1) containing the polar solvent, which is recycled as stream 5 to the hydrogenation reactor 1-1, and into a biphasic mixture (S1) containing an upper phase ( 02) containing the tertiary amine (A1) and the lower phase (U2) containing the formic acid-amine adduct (A2).
  • the bottoms mixture (S1) is fed as stream 6 to the third phase separation device 111-1 of the thermal splitting unit.
  • the bottom mixture (S1) is separated to obtain a top phase (03) containing the tertiary amine (A1) and a bottom phase (U3) containing the formic acid-amine adduct ( A2).
  • the upper phase (03) is recycled as stream 10 to the hydrogenation reactor 1-1.
  • the lower phase (U3) is supplied as stream 7 to the second distillation device IV-1 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-1 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a two-phase bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 9 from the distillation apparatus IV-1.
  • the two-phase bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) is recycled as stream 8 to the third phase separator 111-1 of the thermal splitter unit.
  • the sump mixture (S2) is separated into upper phase (03) and lower phase (U3).
  • the upper phase (03) is recycled as stream 10 to the hydrogenation reactor 1-1.
  • the lower phase (U3) is recycled as stream 7 to the second distillation device IV-1.
  • a stream 11 containing carbon dioxide and a stream 12 containing hydrogen are fed to a hydrogenation reactor I-2. It is possible to supply the hydrogenation reactor I-2 with further streams (not shown) in order to compensate for any losses of the tertiary amine (A1) or of the catalyst which may occur.
  • carbon dioxide and hydrogen are reacted in the presence of a tertiary amine (A1), a polar solvent and an iron complex compound as a catalyst.
  • a two-phase hydrogenation mixture (H) which has an upper phase (01) comprising the catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2 ) contains.
  • the hydrogenation mixture (H) is fed as stream 13a to a first phase separation device V-2.
  • the hydrogenation mixture (H) is separated into the upper phase (01) and the lower phase (U 1).
  • the upper phase (01) is recycled as stream 22 to the hydrogenation reactor I-2.
  • the lower phase (U 1) is supplied as stream 13b of the extraction unit VI-2.
  • the lower phase (U 1) is extracted with the tertiary amine (A1), which is recycled as stream 20 (upper phase (03)) from the third phase separator II I-2 to the extraction device VI-2.
  • a raffinate (R2) and an extract (E2) are obtained.
  • the raffinate (R2) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 13c to the first distillation apparatus I I-2.
  • the extract (E2) contains the tertiary amine (A1) and the residues of the complex catalyst and is recycled as stream 21 to the hydrogenation reactor I-2.
  • the raffinate (R 2) is separated into a distillate (D 1) containing the polar solvent, which is recycled as stream 15 to the hydrogenation reactor I-2, and into a biphasic sump mixture (S 1).
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2).
  • the bottoms mixture (S1) is fed as stream 16 to the second distillation device IV-2.
  • the formic acid-amine adduct present in the bottom mixture (S1) is cleaved in the second distillation device IV-2 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 19 from the second distillation device IV-2.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) is added as stream 18 to the third phase separation device 111- 2 of the thermal splitting unit recycled.
  • the sump mixture (S2) is separated to obtain an upper phase (03) containing the tertiary amine (A1) and a lower phase (U3) containing the formic acid-amine adduct (A2).
  • the upper phase (03) is recycled from the third phase separator II I-2 as stream 20 to the extraction unit VI-2.
  • the lower phase (U3) is supplied as stream 17 to the second distillation device IV-2 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-2 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottom mixture (S2) are again obtained.
  • Transition metal complex compound A 100 mL and a 250 mL autoclave made of Hastelloy C (hydrogenation reactor) equipped with a paddle stirrer was charged under inert conditions with the tertiary amine (A1), the polar solvent and the catalyst. Subsequently, the autoclave was sealed and carbon dioxide was pressed at room temperature. Subsequently, hydrogen (H 2 ) was pressed on and the reactor was heated with stirring (1000 rpm). After the reaction time, the autoclave was cooled and the hydrogenation mixture (H) was decompressed, water was added and stirred for 10 minutes at room temperature.
  • Hastelloy C hydrogenation reactor
  • a biphasic hydrogenation mixture (H) was obtained in which the upper phase (01) was enriched with the free tertiary amine (A1) and the catalyst and the lower phase (U 1) with the polar solvent and the formic acid-amine adduct (A2) formed was.
  • the phases were then separated.
  • the formic acid content (in the form of the formic acid-amine adduct (A2)) of the lower phase (U 1) and the ruthenium content (C Ru ) of both phases was determined by the methods described below.
  • the upper phase (01) containing ruthenium catalyst was then supplemented with fresh tertiary amine (A1) to 85 g and re-used for C0 2 hydrogenation with the same solvent under the same reaction conditions as before (see A1 -b and A2-b).
  • the total content of formic acid in the formic acid-amine adduct (A2) was determined by titration with 0.1 N KOH in MeOH potentiometrically with a "Mettler Toledo DL50" titrator
  • the ruthenium content was determined by AAS The parameters and results of the individual Experiments are shown in Table 1.
  • the comparative examples (A1 -a and A1-b) and the inventive examples (A2-a, A2-b, A3-a and A3-b) show that the catalyst can be recycled to the C0 2 hydrogenation and reused there.
  • the transition metal complex compounds used according to the invention as catalyst can be depleted by phase separation down to less than or equal to 1 ppm.
  • Comparative Example A1-a First Comparative Example A1-b Inventive Example A2-a (First Inventive Example A2-b Hydrogenation) (Reuse of the Hydrogenation) (Reuse of the Catalyst and
  • Tertiary amine (A1) 85.0 g trihexylamine upper phase from A1 -a to 85 g 85.0 g trihexylamine upper phase from A2-a to 85.0 g supplemented with fresh trihexylamine fresh Trihexylamin added

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CA2854047A CA2854047A1 (en) 2011-11-10 2012-11-07 Process for preparing formic acid by reaction of carbon dioxide with hydrogen
EP12783595.7A EP2776448A1 (de) 2011-11-10 2012-11-07 Verfahren zur herstellung von ameisensäure durch umsetzung von kohlendioxid mit wasserstoff
CN201280054841.XA CN103917551A (zh) 2011-11-10 2012-11-07 通过二氧化碳与氢气反应制备甲酸的方法
IN3469DEN2014 IN2014DN03469A (ja) 2011-11-10 2012-11-07
RU2014123397/04A RU2014123397A (ru) 2011-11-10 2012-11-07 Способ получения муравьиной кислоты путем взаимодействия диоксида углерода с водородом
BR112014010923A BR112014010923A2 (pt) 2011-11-10 2012-11-07 processo para a preparação de ácido fórmico, complexo de metal de transição, e, uso de um complexo de metal transição
KR1020147012260A KR20140090183A (ko) 2011-11-10 2012-11-07 이산화탄소와 수소의 반응에 의한 포름산의 제조 방법
SG11201401103YA SG11201401103YA (en) 2011-11-10 2012-11-07 Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen
JP2014540431A JP2015502922A (ja) 2011-11-10 2012-11-07 二酸化炭素と水素との反応によるギ酸の製造方法
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US9428438B2 (en) 2012-11-27 2016-08-30 Basf Se Process for preparing formic acid
CN113557223A (zh) * 2019-03-08 2021-10-26 日东电工株式会社 甲酸的制造方法

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EP3936498A4 (en) * 2019-03-08 2022-12-14 Nitto Denko Corporation PROCESS FOR THE PRODUCTION OF FORMIC ACID
CN115279723A (zh) * 2020-03-17 2022-11-01 日东电工株式会社 甲酸盐的制造方法及甲酸盐制造系统

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US9428438B2 (en) 2012-11-27 2016-08-30 Basf Se Process for preparing formic acid
CN113557223A (zh) * 2019-03-08 2021-10-26 日东电工株式会社 甲酸的制造方法

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